Brown sulfur dye and process of making same.



UNITED STATES PATENT @FFICE.

CHRISTOPHER RIS, OF BASLE, SlVITZERLAND, ASSIGNOR, BY MESNE ASSIGN- MENTS, TO ANILINE COLOR & EXTRACT WORKS, (FORMERLY JOHN R.

en-rev.

BROWN SULFUR DYE AND PROCESS OF MAKING SAME.

si ncmrcntrron forming part of Letters Patent no. 688,885, dated December 17, 1901.

Application filed February 16, 1901. Serial No. 47,557. (Specimens-l mordanted cotton in brown shades, which are produced by melting metatoluylenediamin together with a suitable dicarboxylic acid of the general formula coon ooon,

wherein R stands, for instance, forphenylen, ethylon, or analogous residues and with polyzo sulfids of alkali.

acids may be used: phtalic acid or its anhydrid, succinic acid or its anhydrid, thiodiglycolic acid, and oxalic acid.

The manufacture of the coloring-matters can be performed in two ways-that is to say, either the metatoluylenediamin may first be transformed into an acidyl derivative by melting the same with the dicarboxylic acid or the latter may directly be added to the mixture of metatoluylenediamin with the polysulfid of alkali. In both cases the best proportions which seem to correspond with the chemical process are those of two molecules of metatoluylenediamin and one mole- 3 5 cule of the dicarboxylic acid; but they may always be varied within certain limits. Instead of metatoluylenediamin a nitro compound may be used, which by a treatment with reducing agents furnish this base-viz.,

4o ortho-nitro-para toluidin or para-nitro-ortl1otoluidin.

The following, examples may be given to illustrate the process of carrying out the invention; A

Example I: Thirty-four kilograms of metatoluylenediamin and twenty kilograms of phtalic-anhydrid are melted together at about 120 to 200 centigrade till the development of aqueous vapor is finished. Then the melt is introduced into a fusion of forty kilograms of sulfur in one hundred and twenty kilo- The following dicarboxylic grams of sodium sulfid. Then the mixture is heated up to 270 to 300 centigrade till the development of sulfureted hydrogen will be finished and an augmentation of the coloring-matter can no more be observed. The process is carried out in an iron vessel fitted with a stirring mechanism. The melt is then pulverized.

Example II: Twenty kilograms of ortho- 6o 11itro-para-toluidin are melted With twenty kilograms of phtalic anhydrid at about 150 to 170 centigrade till the development of aqueous vapor is finished. Then the melt is introduced into a fusion of forty kilograms of sulfur in one hundred and twenty kilograms of sodium sulfid. Then seventeen kilograms of metatoluylenediamin are added and the whole treated as described in Example I.

Example III: Thirty -four kilograms of metatoluylenediamin are introduced into a fusion of forty kilograms of sulfur in one hundred and twenty kilograms of sodium sulfid. Then a solution of twenty-eight kilo- 7 5 grams of thiodiglycolate of sodium (see p. e. Lovn, Berichtc der Dcutschen Chemt'schen Gesellschafl, Vol. XVII, page 2818) in about one hundred liters of water is added and the Whole treated as described in the first ex- 8e ample.

Example 1V: Thirty four kilograms of metatoluylenediamin and seventeen rkilograms of oxalic acid are melted together and heated to about 200 centigrade till the development of aqueous vapor is finished and then treated with a fusion of forty kilograms of sulfur in one hundred and twenty kilograms of sodium sulfid, as described in the first example.

In these examples instead of a fusion of sulfur with sodium sulfid a solution of sulfur in causticsoda lye may be used.

The new coloring-matters form dark powders easily soluble in water with orange-brown 9 5 color, soluble in alcohol with yellow to orange color and in concentrated sulfuric acid with yellow to orange-brown color, insoluble in ether and benzene. The watery solution yields by addition of acidsa dark-brown prexoo cipitate of the free color acid, which is soluble in a boiling solution of carbonate of so diurn with orange-brown color. When treated with reducing agents, such as powder of zinc and hydrochloric acid, the color acid generates sulfureted hydrogen.

The new coloring-matters dye unmordanted cotton in a bath containing sodium sulfid and salt bright orange-brown shades, which by means of oxidation on the fiber turn into yellowish brown of great fastness to light, alkalies, acids, and to soap.

Having thus described my invention, I claim as new and desire to secure by Letters Patent- 1. The process for the manufacture of new brown sulfur dyestuffs,which consists in melting metatoluylenediamin together with a suitable dicarboxylic acid of the general formula I COO I R ooorr 3. As new articles of manufacture the here= in-described brown coloring-matters, forming dark powders, easily soluble in water with orange-brown color, soluble in concentrated sulfuric acid with yellow to orange-brown color, soluble in alcohol with yellow to orange color, insoluble in ether and benzene, the watery solution being precipitated by addition of acids in dark-brown flocks of the free color acid, which is soluble in a boiling solution of carbonate of sodium with orange-brown color and which when treated with reducing agents, such as powder of zinc and hydrochloric acid, generates sulfureted hydrogen, the new coloring-matters dyeing unmordanted cotton in a bath containing sodium sulfid and salt bright, orange-brown shades, which by means of oxidation on the fiber turn into yellowish brown of great fastness to light, alkalies, acids and soap, substantially as set forth.

In testimony that I claim the foregoing as my invention I have signed my name in presence of two subscribing witnesses.

CHRISTOPHER RIS.

Witnesses ALBERT GRAETER, GEORGE GIFFORD. 

